EP3703479B1 - Matériau composite pour blinder les rayonnements électromagnétiques, matière première destinée à des procédés de fabrication d'additifs et produit comprenant ce matériau composite et son procédé de fabrication - Google Patents

Matériau composite pour blinder les rayonnements électromagnétiques, matière première destinée à des procédés de fabrication d'additifs et produit comprenant ce matériau composite et son procédé de fabrication Download PDF

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EP3703479B1
EP3703479B1 EP19461516.7A EP19461516A EP3703479B1 EP 3703479 B1 EP3703479 B1 EP 3703479B1 EP 19461516 A EP19461516 A EP 19461516A EP 3703479 B1 EP3703479 B1 EP 3703479B1
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Prior art keywords
nanoparticles
graphene
electromagnetic radiation
composite
shielding
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German (de)
English (en)
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EP3703479A1 (fr
Inventor
Mariusz Zdrojek
Jaroslaw Judek
Krzysztof Jakubczak
Anna Duzynska
Klaudia Zeranska-Chudek
Anna Wroblewska
Anna Lapinska
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Nanoemi SpZ OO
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Nanoemi SpZ OO
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Priority to ES19461516T priority Critical patent/ES2939245T3/es
Priority to EP19461516.7A priority patent/EP3703479B1/fr
Priority to PL19461516.7T priority patent/PL3703479T3/pl
Priority to AU2020201098A priority patent/AU2020201098A1/en
Priority to CA3073670A priority patent/CA3073670A1/fr
Priority to KR1020200023735A priority patent/KR20200105625A/ko
Priority to US16/803,511 priority patent/US11766854B2/en
Priority to CN202010125377.5A priority patent/CN111621072A/zh
Priority to BR102020003875-3A priority patent/BR102020003875A2/pt
Priority to MX2020002248A priority patent/MX2020002248A/es
Priority to JP2020031334A priority patent/JP2020143275A/ja
Publication of EP3703479A1 publication Critical patent/EP3703479A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H05K9/0083—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive non-fibrous particles embedded in an electrically insulating supporting structure, e.g. powder, flakes, whiskers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2274/00—Thermoplastic elastomer material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/212—Electromagnetic interference shielding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • G—PHYSICS
    • G12—INSTRUMENT DETAILS
    • G12B—CONSTRUCTIONAL DETAILS OF INSTRUMENTS, OR COMPARABLE DETAILS OF OTHER APPARATUS, NOT OTHERWISE PROVIDED FOR
    • G12B17/00—Screening
    • G12B17/02—Screening from electric or magnetic fields, e.g. radio waves

Definitions

  • the object of the invention is a composite material for shielding electromagnetic radiation, a raw material for additive manufacturing methods and a product comprising the material as well as a method of manufacturing the product.
  • the composite material according to the invention can serve as a material protecting electronic elements, electronic devices or living organisms from electromagnetic radiation in the microwave and terahertz range (0.3-10000 GHz).
  • electromagnetic interference mainly in the range of radio and microwave waves, but also increasingly in the terahertz range of 100 - 0.03 mm, usually defined in the frequency range of 0.3-10000 GHz.
  • This radiation may have a negative impact on both the operation of electronic devices and living organisms, including humans.
  • the following examples can be given: failure of medical equipment monitoring signals of the human body, mass transit systems or air/car transport suffering from the failure of sensitive electrical devices, interference in audio/video/GPS signals in various telecommunications systems. Therefore, there is a need for effective blocking of or shielding this type of radiation, which is extremely important in many industries and for ordinary consumers. This problem is usually defined as electromagnetic interference (EMI).
  • EMI electromagnetic interference
  • the EMI problem can be solved using a shield and can be physically realised by absorbing and/or reflecting electromagnetic radiation by a material which acts like a shield.
  • the relationship between shielding effectiveness (in units of dB) and shielding efficiency in % is following: effectiveness of 10 dB means that 90% of the incident electromagnetic radiation power is stopped by the material. Going further, by analogy: 20dB - 99%, 30dB - 99.9%, 40dB - 99.99%, 50dB - 99.999%, 60dB- 99.9999%.
  • metal is the most commonly used shielding material. It is, however, a non-selective material which simultaneously shields electromagnetic radiation in a very wide range of the spectrum, including the microwave and terahertz range. It is noteworthy that metal is a material which mainly reflects and does not absorb radiation. Furthermore, metal cannot always be used due to the fact that it is an electrically conductive material, poorly plastic and inflexible and usually has a high specific gravity.
  • Conductive polymer composites with metal fillers are known, which can be used as EMI shielding materials, like a composite filled with aluminium or stainless steel flakes (up to 40%), characterised by shielding effectiveness higher than 50 dB ( Composites 25, 215, 1994 ). It has been proven that mixing aluminium powder with a PVDF polymer, followed by hot pressing gives a shielding composite in the range of 8-12 GHz at the level of ⁇ 20 dB ( Journal of Applied Physics 117, 224903 2015 ). Composites containing silver nanowires ( ⁇ 14 vol.%) as a filler, produced by instillation, also exhibit shielding properties (50 dB, 8-12 GHz) ( J. Mater.
  • the material absorbing electromagnetic radiation in the microwave range is carbon as such in various forms: graphite, carbon nanotubes and graphene.
  • Graphene is a carbon allotrope with a two-dimensional hexagonal structure.
  • carbon nanotubes consist of one or more graphene monolayers rolled up in the shape of coaxial cylinders with diameters of 0.5 to several dozen nanometres and lengths up to several centimetres.
  • thin and large surface layers of reduced graphene oxide, forming a laminate with a thickness of 10 ⁇ m have a shielding ability of 20 dB in the 1-4 GHz range ( Carbon 94, 494, 2015 ).
  • Another example is thin graphene layers with an admixture of magnetic nanoparticles, e.g.
  • Fe 3 O 4 prepared by filtration from a suspension with an admixture of ferrites. These layers achieved a shielding effectiveness of ⁇ 20dB in the 8-12 GHz range ( J. Mater. Chem. A 3, 2097, 2015 ). These materials are electrically conductive in the DC range, and the shielding mechanism is based on the existence of metallic paths in the material.
  • Polymer composites with nanocarbon fillers having shielding properties are also known, such as a composite containing an admixture of multi-wall carbon nanotubes in a polypropylene matrix.
  • the composite has shielding properties in the range of 8-12 GHz at the level of 30dB at an admixture concentration of ⁇ 7%.
  • the composite was prepared by dry direct mixing of the ingredients at room temperature, and then the obtained powder was melted and compressed into thin plates ( Carbon 47, 1738, 2009 ).
  • the composite is conductive in the DC range.
  • a foam composite based on polystyrene and carbon nanotubes is also known, exhibiting a shielding property in the range of 8-12 GHz reaching almost 20 dB.
  • the composite was prepared by mixing the filler in a solution of toluene with polystyrene containing a foaming agent and by spraying the suspension mixed in this manner, wherein in the next stage the foam concentrate was removed hot ( Nano Letters 11, 2131, 2005 ).
  • the composite is conductive in the DC range.
  • Graphene are also used in polymer composites as fillers, acting as an active element shielding electromagnetic radiation.
  • a porous composite which consists of polystyrene and functionalised graphene (up to 30% by weight) and exhibits a shielding efficiency up to 30dB in the 8-12 GHz range.
  • the composite was prepared by direct mixing of ingredients and hot pressing and by using a process that forms a porous structure ( J. Mater. Chem., 22, 18772, 2012 ).
  • the composite is conductive in the DC range.
  • a method for producing a conductive (in the DC range) composite based on thermally reduced graphene oxide, achieving a shielding ability of 30 dB at low filler concentration ( ⁇ 1%) is also known.
  • the composite was prepared by mechanical mixing of graphene oxide and polyethylene granules which were then subjected to hot compression. Importantly, this process resulted in simultaneous reduction of graphene oxide ( Nanotechnology 25, 145705, 2014 ).
  • Polymeric materials with an admixture of two-dimensional structures of carbides/nitrides of rare earth metals are also disclosed.
  • the use of Ti 3 C 2 T x , Mo 2 TiC 2 T x , Mo 2 Ti 2 C 3 T x structures in form of thin layers and polymer composites (sodium aluminate) produced from the suspensions of these compounds by the vacuum filtration method is known. These materials have excellent shielding properties, exceeding 50 dB ( Science 353, 1137, 2016 ).
  • the composite is conductive in the DC range.
  • Polymer composites with nanocarbon fillers are also known.
  • Publication by A. Das et al. (Appl. Phys. Lett. 98, 174101, 2011 ) refers to a polymer composite containing an admixture of carbon nanostructures having the characteristics of a hydrophobic material.
  • the composite exhibits shielding properties at 32 dB in a narrow range of 0.57-0.63 THz.
  • the composite contains a mixture of carbon fibres and several polymers, and it was obtained by adding a homogeneous suspension of nanostructures in acetone to the polymer mixture, and then slowly drying.
  • the material having these shielding parameters was conductive ( ⁇ 10 3 S/m).
  • WO 201253063 discloses a method for preparing polymer-carbon composites containing various forms of nanocarbon, preferably carbon nanotubes.
  • the material is prepared by preparing a pre-mix comprising from 3% to 50% by weight of carbon nanoparticles and at least one polymeric binder.
  • carbon nanoparticles and the binder are mixed until a stable polymer emulsion or suspension in the aqueous phase is obtained.
  • a material matrix is a thermosetting polymer
  • the concentrated pre-mix is dispersed in a matrix of this polymer, such as e.g.: bisphenol, epoxy resin, vinyl ester resin, unsaturated polyester, polyol, polyurethane.
  • the polymer-specific hardener is then added to the mixture in order to obtain a finished composite material.
  • the introduction of carbon nanotubes in form of a concentrate allows to obtain a homogeneous distribution of nanotubes in the material, and therefore better electrical conductivity.
  • the material according to this application was characterised by properties of radiation attenuation only up to 0.1THz.
  • US8610617 proposes the use of individual large-format graphene layers applied one by one to an object to be protected from electromagnetic radiation in the microwave and terahertz range through its absorption. It is also disclosed that graphene can be used in form of paint or fabric and used to cover the object. The material is conductive in the DC range.
  • US 9215835 discloses a method of protecting an object from electromagnetic radiation for frequencies higher than 1MHz directed directly at the object, by directly covering the object with layers of graphene one by one, being in contact with each other, wherein at least one of said layers is doped with inorganic acids or/and metal salts.
  • the proposed solution exhibits a radiation shielding ability at a level above 30 dB.
  • CN 103232637 discloses a conductive composite comprising 92.5-97.5 parts by weight of polypropylene, 1-3 parts by weight of graphene and 1.5-4.5 parts by weight of polypropylene grafted with maleic anhydride.
  • the material obtained is used as a conductive material or a material shielding electromagnetic radiation.
  • a conductive (DC) panel absorbing electromagnetic radiation consisting of a dielectric separator with a low relative dielectric permittivity and an inhomogeneous resistive layer.
  • the resistive layer is formed by at least one layer of a polymer composite comprising 1-80 wt% of graphene nanoflakes with an average diameter of 2-25 ⁇ m and a thickness of up to 10 nm, applied to a thin polymer film by means of the screen printing technique.
  • WO2018081394A1 discloses a composite shielding against electromagnetic radiation, comprising about 5-50 wt% of matrix material having a low dielectric loss, such as, in particular, polysiloxane, but also polyethylene, polystyrene, polypropylene, poly(phenylene sulphide), polyimide, poly(ethylene terephthalate), butyl rubber, terpolymer of acrylonitrile-butadiene-styrene (ABS), polycarbonate or polyurethane, and about 50-95 wt% of copper oxide CuO particles dispersed in a matrix material.
  • this composite may also contain 0.1-10 wt% of electrically conductive fillers, such as, e.g.
  • a relatively high content of CuO particles (at least 50 wt%, preferably 70 wt%) is a necessary element, while the optional addition of electrically conductive filler selected from a number of very different carbonaceous, metallic and polymeric materials does not exceed 10 wt%, and preferably it is a carbon black in an amount of 0.3 to 4 wt%.
  • the composite is intended for shielding, mainly by absorption, of electromagnetic radiation in the range of about 0.01-100 GHz.
  • WO2018081394A1 lacks detailed information on the type, content and form of an optional conductive additive of carbon filler other than carbon black, as well as on shielding efficiency.
  • CN104650498B discloses a composite in the form of a thin conductive layer, containing graphene in an amount of 0.5-5 wt% dispersed in a polymer matrix (e.g. PVC) and forming in it a spatial electrically (DC) conductive network.
  • a polymer matrix e.g. PVC
  • DC spatial electrically
  • a composition for dissipation of energy at least in the range of about 1-20 GHz, containing graphene in a dielectric matrix, such as a thermoplastic polymer, preferably ABS, wherein the graphene content is preferably about 5-20%, in particular 15-20% by volume of the composition.
  • a dielectric matrix such as a thermoplastic polymer, preferably ABS
  • the graphene content is preferably about 5-20%, in particular 15-20% by volume of the composition.
  • US9252496B2 contains no mention of the form of graphene used, shielding efficiency, nor the use of any additive introducing dielectric loss unrelated to electrical conductivity, nor agents allowing to control graphene dispersion in a polymer matrix.
  • CN103232637B describes a conductive nanocomposite material containing 92.5-97.5 parts by weight of polypropylene as a matrix, 1-3 parts by weight of graphene as a conductive filler and 1.5-4.5 of polypropylene grafted by maleic anhydride as a graphene dispersion promoter.
  • CN103232637B only briefly mentions the shielding of electromagnetic radiation without specifying any range or determining the efficiency of shielding, or the use of any additive introducing dielectric loss unrelated to electrical conductivity, or the specific form of graphene used. The experimental results provided are limited solely to the study of conductivity which generally increases with the participation of graphene.
  • the aim of the invention was to provide a flexible and light composite material which allows shielding of electromagnetic radiation over a wide frequency range, i.e. in the microwave and terahertz range (0.3-10000 GHz) with an efficiency exceeding 10dB (per millimetre of thickness) at least in part of this range. It was a further aim of the invention that such a composite material, by appropriately selecting a particular composition and manufacturing method, would allow to control the dominant shielding mechanism (reflection, absorption) and a particular range of shielded electromagnetic field. It was another aim of the invention that an appropriate selection of a particular composition and method of manufacturing the composite would allow to obtain a material conducting or not conducting direct current, as well as selective shielding efficiency, different in different ranges of electromagnetic radiation.
  • the object of the invention is a composite material for shielding electromagnetic radiation, comprising:
  • the composite material according to the invention allows to shield electromagnetic radiation with a frequency in the microwave and terahertz range (0.3-10000 GHz) with an efficiency exceeding 10dB (per millimetre of thickness) in at least part of this range.
  • the form of nanocarbon material - flakes having a diameter to thickness ratio higher than 3, the thickness of the flakes being not larger than 30 nm, and the diameter being of 100 to 5000 nm - provides a quasi-two-dimensional charge distribution in each nanocarbon object separately and easier formation of percolation paths in the polymer matrix which facilitate the transport of charge and heat, and allows to obtain a material conducting or not conducting direct current.
  • the specific type and proportion dielectric nanoparticles introducing a loss unrelated to electrical conductivity in a given frequency range, and in particular having a ferromagnetic resonance frequency adequate to the band for which attenuation is to be significant is an important parameter allowing to control the dominant shielding mechanism (reflection, absorption) and a specific range of shielded electromagnetic field, as well as selective shielding efficiency for a given radiation range.
  • the thermoplastic polymer is selected from polystyrene (PS), polyethylene (PE), polypropylene (PP), polyurethane (PU), terpolymer of acrylonitrile-butadiene-styrene (ABS), a polyester such as, in particular, poly(ethylene terephthalate) (PET), poly(tetrafluoroethylene) (PTFE), polyamide (PA), terpolymer of acrylonitrile-styrene-acrylic (ASA), poly(vinyl chloride) (PVC), modified poly(phenylene ether) (MPPE), incombustible and self-extinguishing LSZH plastic (Low Smoke Zero Halogen), a derivative of one of these polymers or a combination thereof.
  • PS polystyrene
  • PE polyethylene
  • PP polypropylene
  • PU polyurethane
  • ABS terpolymer of acrylonitrile-butadiene-styrene
  • ABS a polyester
  • the nanocarbon material is selected from flake graphene, graphene oxide, reduced graphene oxide, modified flake graphene, nanographite or a combination thereof.
  • the nanoparticles are dielectric particles having a ferromagnetic resonance frequency (adequate to the band for which attenuation is to be significant) and/or an anisotropy coefficient of magnetic and/or electrical permittivity, and/or a dielectric loss for an alternating electromagnetic field (EM) resulting from the polarisation of components constituting the particle.
  • EM alternating electromagnetic field
  • the nanoparticles are selected from nanoparticles of silicon carbide (SiC), aluminium oxide (Al 2 O 3 ), Fe-BN, ferrite-based nanoparticles, preferably having hexagonal structure, containing cobalt or barium, or strontium, preferably CoFe 2 O 4 , BaFe 12 O 19 , SrFe 12 O 19 , Ba 3 Me 2 Fe 24 O 41 , Ba 3 Sr 2 Fe 24 O 41 , Ba 2 Co 2 Fe 12 O 22 , BaCo 2 Fe 16 O 27 , Ba 2 CO 2 Fe 28 O 46 , Ba 4 Co 2 Fe 36 O 60 , or combinations thereof.
  • SiC silicon carbide
  • Al 2 O 3 aluminium oxide
  • Fe-BN Fe-BN
  • ferrite-based nanoparticles preferably having hexagonal structure, containing cobalt or barium, or strontium, preferably CoFe 2 O 4 , BaFe 12 O 19 , SrFe 12 O 19 , Ba 3 Me 2 Fe 24 O 41 , Ba 3 S
  • the auxiliary material is a graphene-functionalising compound, including a plasticiser, an antioxidant, a hardener, or a combination thereof.
  • the plasticiser is an organic oil, an alcohol, an anhydride or a combination thereof.
  • the antioxidant is a natural antioxidant, preferably a carotenoid, a flavonoid, vitamin C, vitamin E, phenols or combinations thereof.
  • the object of the invention is also a raw material for additive manufacturing methods (commonly referred to as 3D printing) of elements for shielding electromagnetic radiation, comprising the material according to the invention as defined above, preferably in the form of a granulate, a filament or a tape.
  • the object of the invention is a product for shielding electromagnetic radiation comprising the composite material according to the invention as defined above.
  • the invention also relates to a method for preparing the product according to the invention, i.e. comprising the composite material according to the invention as defined above, said method comprising the steps of:
  • the mixing step (i) is carried out by dry mechanical mixing at room temperature.
  • the mixing step (i) is carried out by mechanical mixing at a temperature above the polymer flow temperature.
  • the composite material can serve as a material protecting electronic elements, devices, modules and electronic components, electrical wires or living organisms from electromagnetic radiation in the microwave and terahertz range (0.3-10000 GHz).
  • the elements or products shielding electromagnetic radiation from the composite material according to the invention can be manufactured by injection moulding, extrusion or 3D printing.
  • the composite material may be non-conductive or conductive for direct current depending on the percentage composition of the fillers and the premix structure.
  • it may have selective shielding efficiency (different in different ranges), wherein control of the dominant shielding mechanism (reflection, absorption) and the range, in which the electromagnetic field is to be shielded, is carried out through appropriate selection of the composition and manufacturing method.
  • thermoplastic polymer polyethylene (PE) was used as a polymer material, and a flake graphene (2 wt%) was used as a filler.
  • the first sample contained also maleic anhydride (1 wt%) and a negligible amount of nanoparticles based on BaFe 12 O 19 ferrites ( ⁇ 0.05 wt%), while the other one - maleic anhydride (a negligible amount, i.e. ⁇ 0.05 wt%) and 0.5 wt% of nanoparticles based on ferrites (BaFe 12 O 19 ).
  • the materials were prepared using injection technology.
  • the above example illustrates the shielding properties of the materials according to the invention for EM radiation in the microwave range.
  • thermoplastic polymer from the group of polyesters - polyethylene terephthalate (PET) was used a polymer material, and a flake graphene (2 wt%) and minimum amounts of SrFe 12 O 19 nanoparticles ( ⁇ 0.1 wt%) and maleic anhydride ( ⁇ 0.1 wt%) were used as a filler, and the material was prepared by injection technology.
  • Graphene was added to the polymer when it was in a liquid state (i.e. above 265 ° C) and hot mixed using an extruder and hot extrusion technique. The material was then hot pressed into a mould, the filling of which yielded a thin plate having a thickness of about 1.8 mm, and then cooled.
  • Transmission level (logarithmic scale) of electromagnetic radiation in the range of 0.1-1.8 GHz was also measured ( Fig. 2b ), demonstrating that in this range the material is permeable to the above-mentioned range and thus demonstrating selectivity of shielding efficiency in various ranges.
  • the tested material did not conduct direct current (DC) and its resistivity exceeded 36 ⁇ 10 6 ⁇ cm.
  • a composite comprising polyethylene (PE), a filler in form of flake graphene (2 wt%), maleic anhydride (1 wt%) and a negligible amount ( ⁇ 0.1 wt%) of BaFe 12 O 19 dielectric nanoparticles was obtained analogously to Example 1, producing samples in form of 1 mm thick plates.
  • samples of a comparative composite made of polyethylene and flake graphene (2 wt%) and negligible amounts of anhydride and nanoparticles ( ⁇ 0.05% by weight) were obtained. Electrical conductivity of both composites in various ranges was measured. In the DC range, the current-voltage characteristics for the distance of electrodes equal to 1 mm (curves in Fig.
  • the composite is conductive or non-conductive at different frequency ranges.
  • a composite comprising polyethylene (PE), a filler in form of flake graphene (2 wt%) having two different diameters (5 ⁇ m and 25 ⁇ m), maleic anhydride (1 wt%) and a negligible amount ( ⁇ 0.1 wt%) of BaFe 12 O 19 nanoparticles was obtained analogously to Example 1. Plates having a thickness below 1 millimetre were made from the composites, and their resistivity in various ranges was examined, as illustrated in the following table 1.
  • Table 1 Resistivity values for composite samples from Example 4 Composite Direct Current Alternating Current (5 GHz) With graphene flakes having a diameter of 5 ⁇ m -10 MOhm 200 Ohm/sq With graphene flakes having a diameter of 25 ⁇ m non-conductive (unmeasurable) 700 Ohm/sq
  • the above example illustrates the effect of the size of graphene flakes on whether the composite material according to the invention is conductive or non-conductive at different frequency ranges.

Claims (13)

  1. Un matériau composite pour le blindage d'un rayonnement électromagnétique, ledit matériau contenant un polymère thermoplastique non électriquement conducteur, un matériau nanocarboné et des nanoparticules, caractérisé en ce que le matériau composite comprend:
    • 88 - 99,88 % en poids du polymère thermoplastique électriquement non conducteur;
    • 0,1 - 10 % en poids du matériau nanocarboné, qui est sous forme de flocons ayant un rapport diamètre sur épaisseur supérieur à 3, l'épaisseur des flocons n'excédant pas 30 nm et le diamètre étant de 100 à 5000 nm;
    • 0,01 à 1 % en poids de nanoparticules diélectriques introduisant une perte sans rapport avec la conductivité électrique dans une gamme de fréquence donnée, c'est-à-dire sans rapport avec la dispersion d'une onde électromagnétique sur des porteurs libres ;
    • 0,01 - 1 % en poids d'un matériau auxiliaire qui permet de contrôler la dispersion du matériau nanocarbone et des nanoparticules diélectriques dans une matrice polymère et/ou qui peut modifier les propriétés du matériau nanocarbone et des nanoparticules diélectriques;
    dans lequel le matériau composite se présente sous la forme d'un mélange homogène.
  2. Le matériau selon la revendication 1, dans lequel le polymère thermoplastique est choisi parmi le polystyrène (PS), le polyéthylène (PE), le polypropylène (PP), le polyuréthane (PU), le terpolymère d'acrylonitrile-butadiène-styrène (ABS), un polyester tel comme notamment le poly(éthylène téréphtalate) (PET), le poly(tétrafluoroéthylène) (PTFE), le polyamide (PA), le terpolymère d'acrylonitrile-styrène-acrylique (ASA), le poly(chlorure de vinyle) (PVC), le poly(phénylène éther) (MPPE), LSZH, un dérivé de l'un desdits polymères ou une combinaison de ceux-ci.
  3. Le matériau selon la revendication 1 ou 2, dans lequel le matériau nanocarboné est choisi parmi le graphène en flocons, l'oxyde de graphène, l'oxyde de graphène réduit, le graphène en flocons modifié, le nanographite ou une combinaison de ceux-ci.
  4. Le matériau selon l'une des revendications 1 à 3, dans lequel les nanoparticules diélectriques sont des particules ayant une fréquence de résonance ferromagnétique (adéquate à la bande pour laquelle l'atténuation doit être significative) et/ou un coefficient d'anisotropie de permittivité magnétique et/ou électrique, et/ou une perte diélectrique pour un champ électromagnétique (EM) alternatif résultant de la polarisation des composants constituant la particule.
  5. Le matériau selon la revendication 4, dans lequel les nanoparticules diélectriques sont choisies parmi les nanoparticules de carbure de silicium (SiC), d'oxyde d'aluminium (Al2O3), Fe-BN, les nanoparticules à base de ferrite, de préférence à structure hexagonale, contenant du cobalt ou du baryum, ou le strontium, de préférence CoFe2O4, BaFe12O19, SrFe12O19, Ba3Me2Fe24O41, Ba3Sr2Fe24O41, Ba2Co2Fe12O22, BaCo2Fe16O27, Ba2Co2Fe28O46, Ba4Co2Fe36O60, ou leurs combinaisons.
  6. Le matériau selon l'une des revendications 1 à 5, dans lequel le matériau auxiliaire est un composé fonctionnalisant le graphène, comprenant un plastifiant, un antioxydant, un durcisseur ou une combinaison de ceux-ci.
  7. Le matériau selon la revendication 6, dans lequel le plastifiant est une huile organique, un alcool, un anhydride ou une combinaison de ceux-ci.
  8. Le matériau selon la revendication 6 ou 7, dans lequel l'antioxydant est un antioxydant naturel, de préférence un caroténoïde, un flavonoïde, la vitamine C, la vitamine E, des phénols ou leurs combinaisons.
  9. Une matière première pour procédés additifs de fabrication d'éléments pour le blindage d'un rayonnement électromagnétique, caractérisée en ce qu'elle comprend le matériau défini dans au moins l'une des revendications 1 à 8, de préférence sous la forme d'un granulat, d'un filament ou d'un ruban.
  10. Un produit pour le blindage d'un rayonnement électromagnétique, caractérisé en ce qu'il comprend le matériau défini dans au moins l'une des revendications 1-8.
  11. Un procédé pour obtenir le produit selon la revendication 10, caractérisé en ce qu'il comprend les étapes consistant à:
    (i) mélanger
    • 88 - 99,88 % en poids d'un polymère thermoplastique électriquement non conducteur, de préférence sous forme de grains d'une taille ne dépassant pas 1 mm,
    • 0,1 - 10 % en poids d'un matériau nanocarboné sous forme de flocons ayant un rapport diamètre sur épaisseur supérieur à 3, l'épaisseur des flocons n'excédant pas 30 nm et le diamètre étant de 100 à 5000 nm,
    • 0,01 - 1 % en poids de nanoparticules diélectriques introduisant une perte sans rapport avec la conductivité électrique,
    • 0,01 - 1 % en poids d'un matériau auxiliaire qui permet de contrôler la dispersion du matériau nanocarbone et des nanoparticules diélectriques dans une matrice polymère et/ou qui peut modifier les propriétés du matériau nanocarbone et des nanoparticules diélectriques;
    (ii) injecter le mélange fondu dans un moule définissant la forme du produit;
    (iii) durcir le matériau pour obtenir le produit fini.
  12. Le procédé selon la revendication 11, dans lequel l'étape de mélange (i) est réalisée par mélange mécanique à sec à température ambiante.
  13. Le procédé selon la revendication 11, dans lequel l'étape de mélange (i) est réalisée par mélange mécanique à une température supérieure à la température d'écoulement du polymère.
EP19461516.7A 2019-02-28 2019-02-28 Matériau composite pour blinder les rayonnements électromagnétiques, matière première destinée à des procédés de fabrication d'additifs et produit comprenant ce matériau composite et son procédé de fabrication Active EP3703479B1 (fr)

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ES19461516T ES2939245T3 (es) 2019-02-28 2019-02-28 Material compuesto para apantallamiento de radiación electromagnética, materia prima para métodos de fabricación aditiva y producto que contiene este material compuesto y método de fabricación de este producto
EP19461516.7A EP3703479B1 (fr) 2019-02-28 2019-02-28 Matériau composite pour blinder les rayonnements électromagnétiques, matière première destinée à des procédés de fabrication d'additifs et produit comprenant ce matériau composite et son procédé de fabrication
PL19461516.7T PL3703479T3 (pl) 2019-02-28 2019-02-28 Materiał kompozytowy do ekranowania promieniowania elektromagnetycznego, surowiec do addytywnych metod wytwarzania i wyrób zawierający ten materiał kompozytowy oraz sposób wytwarzania tego wyrobu
AU2020201098A AU2020201098A1 (en) 2019-02-28 2020-02-14 Composite material for shielding electromagnetic radiation, raw material for additive manufacturing methods and a product comprising the composite material as well as a method of manufacturing the product
CA3073670A CA3073670A1 (fr) 2019-02-28 2020-02-25 Materiau composite pour blindage contre le rayonnement electromagnetique, matiere premiere pour procedes de fabrication additive et produit comprenant le materiau composite ainsi que procede de fabrication du produit
KR1020200023735A KR20200105625A (ko) 2019-02-28 2020-02-26 전자기 방사선을 차폐시키기 위한 복합 재료, 부가적 제조 방법을 위한 원료 및 복합 재료를 포함하는 제품 및 이러한 제품의 제조 방법
US16/803,511 US11766854B2 (en) 2019-02-28 2020-02-27 Composite material for shielding electromagnetic radiation, raw material for additive manufacturing methods and a product comprising the composite material, as well as a method of manufacturing the product
CN202010125377.5A CN111621072A (zh) 2019-02-28 2020-02-27 屏蔽电磁辐射的复合材料、增材制造方法的原材料和包含该复合材料的产品及其制造方法
BR102020003875-3A BR102020003875A2 (pt) 2019-02-28 2020-02-27 material compósito para barreira de radiação eletromagnética, matéria-prima para métodos aditivos de fabricação de elementos para barreira de radiação eletromagnética, produto para barreira de radiação eletromagnética, e, método para obter o produto
MX2020002248A MX2020002248A (es) 2019-02-28 2020-02-27 Material compuesto para el blindaje de la radiacion electromagnetica, materia prima para metodos de fabricacion aditiva y un producto que comprende el material compuesto asi como un metodo de fabricacion del producto.
JP2020031334A JP2020143275A (ja) 2019-02-28 2020-02-27 電磁放射線を遮蔽するためのコンポジット材料、付加製造方法のための原材料及びそのコンポジット材料を含む製品並びにその製品を製造する方法

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AU2020201098A1 (en) 2020-09-17
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US20200276797A1 (en) 2020-09-03
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MX2020002248A (es) 2021-02-09
US11766854B2 (en) 2023-09-26
CN111621072A (zh) 2020-09-04
PL3703479T3 (pl) 2023-03-20

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